Heavy atom isotope effect
Answers
Kinetic Isotope Effects (KIEs) are used to determine reaction mechanisms by determining rate limiting steps and transition states and are commonly measured using NMR to detect isotope location or GC/MS to detect mass changes. In a KIE experiment an atom is replaced by its isotope and the change in rate of the reaction is observed. A very common isotope substitution is when hydrogen is replaced by deuterium. This is known as a deuterium effect and is expressed by the ratio kH/kD (as explained above). Normal KIEs for the deuterium effect are around 1 to 7 or 8. Large effects are seen because the percentage mass change between hydrogen and deuterium is great. Heavy atom isotope effects involve the substitution of carbon, oxygen, nitrogen, sulfur, and bromine, with effects that are much smaller and are usually between 1.02 and 1.10. The difference in KIE magnitude is directly related to the percentage change in mass. Large effects are seen when hydrogen is replaced with deuterium because the percentage mass change is very large (mass is being doubled) while smaller percent mass changes are present when an atom like sulfur is replaced with its isotope (increased by two mass units).